DE1644587C - Anthraquinone dyes and their uses - Google Patents

Description

2. Dye of the formula O NH.

7. Use of the anthraquinone dyes according to the claims! to 6 as dyes door synthetic materials.

8. Use of the dyestuffs according to Claims 1 to 6 for dyeing fiber materials made of aromatic polyesters.

The present invention relates to new anthraquinone dyes of the formula

T-SO ₂ - '

Cl

3. Dye of the formula NH

HO O NH ₂

4. Dye of the formula O NH ₂

SO ₂ -

O NH ₂ 5. Dye of the formula

SO ₂ -OY \

6. Dye of the form ¹

Y ₁ OX ₁

SO ₂ -OR

35

40 in which X ₁ and X _{2 are} a primary amino group or a hydroxyl group, Y ₁ and Y _{2 are} hydrogen, a primary amino group or a hydroxyl group and R tines are optionally substituted by lower alkyl, methoxy, chlorine, bromine, methyl mercapto, nitro, trifluoromethyl, phenyl, acetyl , Carbomethoxy or carboxyl-substituted phenyl radical or a naphthyl radical, and their use for dyeing synthetic materials.

The new dyes are obtained, for example, by adding the anthraquinone sulfonic acid halides formula

Y, O

O X

HO O NH ₂

in which X ₁ , X ₂ , Y ₁ and Y _{2 have} the abovementioned meaning and Z stands for a halogen atom, with phenols of the formula ROH, in which R has the abovementioned meaning, and then, if the anthraquinone radical does not have at least two auxochromic groups contains, introduces a corresponding number of auxochrome groups into the anthraquinone residue by known methods.

Examples of the anthraquinone sulfonic acid halides used as the starting material are particularly the corresponding anthraquinone sulfonic acid chlorides, such as the following: 1,4-diamino-anthraquinone - 2 - sulfochloride, 1,4 - dihydroxy - anthraquinone-2 - sulfochloride, 1,5 - dihydroxy -4,8 - diamino - anthraquinone - 2 - sulfochloride, 1,4-diamino - 5 - hydroxyanthraquinone-2-sulfochloride.

The Anthrachir.onsulfonsäurechloride can by the generally customary methods from the anthraquinonesulphonic acids or their salts with the aid obtained from chlorosulfonic acid, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride.

Examples of the phenols ROH used as starting materials are as follows:

Phenol, p-chlorophenol, m-chlorophenol, o-chlorophenol, p-brompheno !. O-. m-, p-cresol, 2,4-dichlorophenol, 3.4 - dimethylphend, 3 - chloro - 6 - methylphenol, ρ - methyl mercaptophene, m - methoxy

phenol, p-methoxyphenol, p-acetylphenol. 3-hydroxybenzoic acid, 4 - Hydroxybenzoic acid methyl ester, ρ - Trifluoromethylphenol 3 - Niirophen'ol, «-Naphthol and // - Naphthol.

The reaction of the anthraquinone sulfonic acid halides can be carried out in an aqueous medium or in an organic solvent, generally with the addition of an acid-binding agent, such as alkali metal hydroxide, alkali metal carbonate or tertiary amine. Examples of organic solvents that may be mentioned are: chlorobenzene, o-dichlorobenzene, nitrobenzene, dimethylformamide, diglycol monomethyl ether and acetone. The reaction can be carried out at room temperature or at higher or lower temperatures, e.g. B. between -20 and + 100 C, preferably at 0 to 60 ⁰ C.

The subsequent introduction of auxochromic groups can be carried out according to generally customary chemical methods Carry out method. So it is B. possible, kernsuiiidiges Exchange halogen for an amino group. Furthermore, nitro groups can become amino groups be reduced. Here, nitro groups and halogens can already be found in the original anhraquinone sulfonic acids be contained or by careful halogenation or nitration of the Anthraquinonesulfonic acid aryl ester are introduced. The following process routes are mentioned as examples: 1-Amino-4-Lrom-anthraquinone-2-sulfonic acid aryl ester are with amines, p-Toluolsiilfamid or Phenyl mercaptans implemented. In the case of the acylamino compound obtained, the tosylamino group also 'hole can still be converted into the amino group by acidic saponification.

According to the method mentioned, for. B. the following dyes are obtained: 1,4-diaminoanthraquinone-2-sulfonic acid (3'-methoxyphenyl ester), 1,4-diamino-anlhraquinone-2-sulfonic acid (3'-chloro-6 '- methyl - phenyl ester), 1,4 - diamino - 5 - hydroxyanthraquinone - 2 - sulfonic acid phenyl ester, 1.5 - dihydroxy - 4,8 - diamino - anthraquinone - 2 - sulfonic acid phenyl ester.

The new dyes of the formula II according to the invention are particularly suitable for coloring and printing of fiber materials made from cellulose esters. synthetic polyamides, polyurethanes, polyacrylonitrile and aromatic polyesters, especially polyethylene glycol terephalates. The dyes can as such or preferably in the form of their aqueous suspension for use. Compared to the underlying, of sulfonic acid phenyl ester groups Free dyes, these new compounds are characterized by improved fastness properties, in particular an improved sublimation simplicity.

Also in comparison with those from Belgian patent specification 627 092 and British patent specification 757 869 Known dyes show the dyes according to the invention in application-related advantages.

So z. B. the 1,4-diaminoanthraquinone-2-sulfonic acid phenyl ester according to the invention compared to the I-amino-anthraquinone-6-sulfonic acid phenyl ester according to British patent specification 757 869 has the advantage of better lightfastness on synthetic polyamide fibers.
Furthermore, for example, the dye according to Example 26 of the present invention is superior to the dye obtained according to the information in Examples 3 and 7 of Belgian patent specification 627 092 with regard to the fastness to sublimation on polyester fibers.
In the following examples, the

"5 given parts by weight and the temperature degrees Ceisius degrees. example 1

In 120 parts of chlorobenzene, 17 parts of the Sodium salt of 3-chloro-6-methyl-phenol and 20 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid chloride registered. The mixture is stirred at 20 to 25 hours for about 15 hours. the reaction product falls mil petroleum ether and stir it with water. 25 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid: re (3'-chloro-6'-methyl-phenyl) ester are obtained.

160 parts of chlorobenzene, 20 parts of 1-amino-4-bromoanthiachinon-2-sulfonic acid (3'-chloro-6'-methylphenyd-ester, 10 parts of p-toluenesulfamide, 3.2 parts of K ₂ CO ₃ and 0.3 parts a mixture of equal parts of copper acetate, Cu ₂ Cl ₂ and copper powder are stirred together 1 to 1V ₂ hours at 120 to Π0 '. it is allowed to crystallize the Reakticnsprodukt, it sucks at 15 to 20 from and is stirred with water and with methanol. 17.5 parts of the 1-amino-4-ρ-toluenesulfamido-anthraquinone-2-sulfonic acid (3'-chloro-6'-methyl-phenyl) ester are obtained. A further amount is obtained from the chlorobenzene filtrate isolate this ester.

In 160 parts of sulfuric acid (96%) at 15 to 25 ° 12 parts of the ester obtained in paragraph 2 are obtained solved. After stirring for 1 hour, the reaction mixture is poured into ice water, filtered off with suction and washed neutral and dries. About 8 parts of 1,4-diaminoanthraquinone are obtained - 2 - sulfonic acid - (3 '- chloro - 6' - methylphenyl) ester.

The dye obtained gives brilliant reddish blue colorations of good to on polyester material very good fastness properties, in particular very good fastness to sublimation.

B e i s ρ i e 1 2 to 9

Analogously to Example 1, the dyes of the following table are obtained, which dye on polyester materials from good to very good fastness properties.

example dye nuance 2
3
4th
5
6th
7th
8th
9 1,4-diamino-anthraquin'in-2-sulfonic acid (3'-methoxyphenyl) ester
1,4-Diamino-anthraquinone-2-sulfonic acid phenyl ester
1,4-diamino-anthraquinone-2-sulfonic acid (4'-chlorophenyl) ester
1,4-diamino-anthraquinone-2-sulfonic acid (2'-chlorophenyl) ester
1,4-diamino-anthraquinone-2-sulfonic acid (3'-chlorophenyl) ester
1,4-diamino-anthraquinone-2-sulfonic acid (4'-bromophenyl) ester
1,4-diamino-anthraquinone-2-sulfonic acid (4'-methylmercapto-phenyl) ester
1,4-diamino-anthraquinone-2-sulfonic acid / i-naphthyl ester Reddish blue
Reddish blue
.Red-tinged blue
Reddish blue
Reddish blue
Reddish blue
Reddish blue
Reddish blue

Example 10

In 120 parts of diethylene glycol monomethyl ether 21.6 parts of sodium phenolate are presented. After at 0 to 5 ° 24.8 parts of l-amino ^ -bromo-S-hydroxyanthraquinone-2-sulfonic acid chloride are entered, the mixture is stirred for 5 hours at 0 to 5 ° and 15 hours 20 to 25 °, diluted with 120 parts of methanol and falls there., Reaction product by slow addition of hydrochloric acid, sucks off and washed with methanol. The filtered off portions are stirred with water, then filtered off again, washed with water and with methanol and dried. 23.8 parts are obtained l-Amino ^ -bromo-S-hydroxy-anthraquinone ^ -sulfonic acid phenyl ester.

160 parts of chlorobenzene, 19.2 parts of 1-amino-4-bromo-5-hydroxy-anthraquinone-2-sulfonic acid phenyl ester. 10 parts of p-toluenesulfamide, 3.2 parts of K ₂ CO ₃ and 0.4 parts of a mixture of equal parts of copper acetate, copper chloride and copper powder are stirred together at 20 for 2 hours. The reaction product is allowed to crystallize, it is filtered off with suction at 15 to 20 and it is stirred with water and with 50% methanol. 16 parts of 1-amino-4-ρ-toluenesulfamido-5-hydroxy-anthraquinone-2-sulfonic acid phenyl ester are obtained.

10 parts of the phenyl ester obtained in the preceding paragraph are dissolved in 15 to 25 parts of sulfuric acid in 180% ^u / oig. After stirring for 1 hour at 20 to 25, the reaction mixture is poured into ice water and, after stirring for 1 hour, is filtered off with suction and the filtered-off components are washed neutral and dried. 7.4 parts of 1,4-diamino-5-hydroxy-anthraquinone-2-sulfonic acid phenyl ester are obtained.

The dye obtained provides blue dyeings with good to very good fastness properties on polyester material.

Example 11

In 100 parts of chlorobenzene, 18 parts of 2.4-dichloro-phenol-sodium are introduced and amino-4-bromo-anthraquinone-2-su fonsäurechlorid added at 20 to 30 '20 parts 1!. After a reaction time of 5 hours at 20 to 25 °, the mixture is diluted with petroleum ether, filtered off with suction and washed with petroleum ether. The filtered off portions are stirred with water, then it is again filtered off with suction, washed with water and with methanol. 25.7 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid (2 ', 4' - dichlorophenyl) ester are obtained. 140 parts of chlorobenzene, 21.2 parts of 1-amino-4-bromo-anthraquinone -2-sulfonic acid (2 ', 4'-dichloropheny! (Ester, 10 parts of p-toluenesulfamide, 3.2 parts of K ₁ CO ₃ and 0, 5 parts of a mixture of equal parts of copper acetate, copper bromur and copper powder are stirred together for 2 hours at 130. The mixture is allowed to crystallize at 15 ° to 20 °, filtered off with suction and washed with petroleum ether Water, washed with methanol and dried. 15 parts of 'amino-4-p-toluene-III-amide' anthraquinone-2-sulfonate (2 ', 4' -dichlorophenyl 'ester. The yield can be considerable by working up the chlorobenzene filtrate increase.

In 180 parts of sulfuric acid of 96% are at 15 to 25 12 parts of the above ester = dissolved. To Stirring for 1 hour at 20 to 25, the reaction mixture is poured into ice water and stirred for 1 hour. sucks off, washes neutral and dries at 80 °. About 8 parts of 1 ^ -diamino-anthraquinone ^ -sulfonic acid (2 ', 4'-dichlorophenyl) ester are obtained.

On polyester materials, the dye gives brilliant reddish blue colorations ranging from good to very good good fastness properties, in particular very good fastness to sublimation.

Example 12 to 19

. The dyes of the are obtained analogously to Example 13 following constitution based on polyester materials Dyeings of good to very good fastness properties result.

example 1,4-diamino 12th 1,4-diamino 13th 1,4-diamino 14th 1,4-diamino 15th i, 4-diamino 16 1,4-diamino 17th ester 1,4-diamino 18th 1,4-diamino 19th ester

dye

• Anthraquinone-2-sulfonic acid (3'-nitro-phenyl) ester

• Anthraquinone-2-sulfonic acid (4'-tert-butyl-phenyl) ester

■ anthraquinone-1-sulfonic acid - ^ '- trifluoromethyl-phenylhester

• Anthraquinone-2-sulfonic acid (4'-phenyl-phenyl) ester

• Anthraquinone-2-sulfonic acid (4'-acetyl-pheny:) ester

• anthraquinone-2-sulfonic acid (3'-methyl-4'-methylmercapto-phenyl) -

• anthraquinone-2-sulfonic acid (4'-caibmethoxy-phenyl) ester ■ anthraquinone-2-sulfonic acid- (3'-methyiensulfon-4'-ether-phenyl) -

nuance

Reddish blue
Reddish blue
Reddish blue
Reddish blue
Reddish blue
Reddish blue

Reddish blue
Reddish blue

Example 20

In 120 parts Diäthylenglykolmonomethylüther 22 parts of sodium phenolate are dissolved at 0 to 5 ■ "18 parts l-amino ^ -bromo-S ^ -dihydroxy-anthraquinone-2-sulionsäurechlorid added. The mixture is then 8 hours at 0 to 5 and ^r for 12 hours at Stirred from 20 to 25 °. The mixture is poured into water, acidified, filtered off with suction and washed neutral. The filtered-off portions are stirred again with water and dried. About 16 parts of 1-amino-4-bromo-5.8 - are obtained. dihydroxy - anthraquinone - 2 - sulfonic acid phenyl ester, which - if desired - can be purified by treating with dimethylformamide and a little water.

90 parts of chlorobenzene, 6 parts of p-toluenesulfamide, 1.8 parts of K ₂ CO ₃ , 9 parts of the ester obtained in paragraph 1 and 0.2 part of a mixture of equal parts of copper acetate, copper bromur and copper powder are stirred for 3 hours at 130 °. It is allowed to crystallize, and at 20 ^{J with} suction. Washes with petroleum ether and stirs the filtered off portions with water

and with methanol. 8.4 parts of 1-amino-4-ρ-toluenesulfamido-5.8-dihydroxy-anthraquinone-2 are obtained - sulfonic acid - phenyl ester.

8.2 parts of the ester obtained in paragraph 2 are dissolved in 100 parts of 96% sulfuric acid at 15 to 25 °. After stirring for 1 hour at 20 to 25 °, the M-diamino-S.S-dihydroxy-anthraquinone-2-sulfonic acid phenyl ester is isolated by slowly adding 50 parts of water while cooling, suctioning off, washing and drying the filter material.

The dye obtained gives greenish blue colorations of good to on polyester materials very good fastness properties.

Example 21

In 100 parts of diethylene glycol monomethyl ether there are 16 parts of the disodium salt of 3-hydroxybenzoic acid submitted. At 15 to 25 "there are 16 parts l-Amino-4-bromo-anthraquinone-2-sulfonic acid chloride entered. The reaction mixture is 8 hours stirred at 20 to 30 °. The melt is then introduced into 440 parts of 4% hydrochloric acid for some time stirred, filtered off with suction and washed. After drying, about 15 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid (3'-carboxy-phenyl) ester are obtained.

120 parts of chlorobenzene. 10 parts of l-amino-4-bromoanthraquinone-2-sulfonic acid (3'-carboxy-phenyl) ester, 5 parts of p-toluoisulfarnide, 3.2 parts of K ₂ CO ₃ and 0.3 part of a mixture of equal parts of copper acetate Copper chloride and copper powder are stirred together for 1 hour at 130 ". It is cooled to 20", poured into petroleum ether, filtered off with suction and washed with petroleum ether. The filtered off portions are stirred with dilute acid, filtered off with suction, washed well with water and methanol and dried. 11.5 parts of 1-amino-4-p-toluenesulfamidoanthraquinone-2-sulfonic acid (3'-carboxy-phenyl) ester are obtained.

In 180 parts of 96% sulfuric acid, 10 parts of the ester described in paragraph 2 are obtained at 10 to 25 " solved. After stirring for 1 hour, the reaction mixture is poured onto ice, filtered off with suction and washed neutral. About 7.3 parts of 1,4-diaminoanthraquinone are obtained - 2 - sulfonic acid (3 '- carboxy - phenyl) ester. The dye yields on polyester materials brilliant reddish blue colorations with good to very good fearfulness properties, especially one very good fastness to sublimation.

Example 22

50 parts of 1,5-dihydroxy-4,8-diamino-anthraquinone-2-sulfonic acid (Na salt) are introduced into 260 parts of chlorosulfonic acid with ice cooling. After adding of 40 parts of thionyl chloride is slowly heated to 70 with stirring. After stirring for 6 hours at 70 "and 2 hours of stirring at 90 ° the cooled Melt was added dropwise to a mixture of 1000 parts of ice and 200 parts of table salt. The secluded The sulfochloride is filtered off with suction and washed several times with a little ice water. The moist Nutschkuchen will stirred into a mixture of 150 parts of sodium phenolate, 500 parts of water and 100 parts of sodium chloride. After stirring for 1 hour at 50, it is filtered off with suction, washed neutral and dried. The raw product is used to remove adhering sulfonic acid in 400 parts Pyridine dissolved hot. After the insoluble fractions have been separated off, 2000 parts of hot water are added diluted. The dye deposited in dark blue needles is filtered off with suction, washed and diluted with Hydrochloric acid freed from adhering pyridine and dried after washing neutral. The thus obtained 1.5 - dihydroxy - 4,8 - diamino - anthraquinone-2-sulfonic acid phenyl ester dyes polyester fiber in clear blue tones with very good lightfastness and sublimation fastness.

Example 23

A blue dye with similar fastness properties is obtained if one takes the place of the 1,5-dihydroxy ^ .S-diamino-anthraquinone-2-sulfonic acid in Example 22 equal parts of 1,8-dihydroxy-4,5-diamino-anthraquinone-2-sulfonic acid (Na salt) cinsets.

Example 24

50 parts of 1,4 - dihydroxy - anthraquinone - 2 - sulfonic acid (Na salt) are introduced into 260 parts of chlorosulfonic acid with ice cooling. After adding 30 parts of thionyl chloride are stirred at 70 for 5 hours and at 80 to 90 for 5 hours. The cooled down Melt is added dropwise with stirring to a mixture of 1000 parts of ice and 200 parts of common salt. The separated sulfochloride is filtered off with suction and washed several times with ice-cold 20% sodium chloride solution and in a mixture of 90 parts of sodium phenate. 60 parts of table salt and 300 parts of water entered. After a reaction time of 2 hours at 50 ", suction is carried out while warm and washed with V.'asscr. The dried crude product is hot in 250 parts of pyridine solved. After the insoluble constituents have been separated off, the mixture is diluted with 700 parts of hot water. The unusual one The dye is filtered off with suction, boiled with dilute hydrochloric acid, filtered off with suction, washed neutral and dried. The 1,4-dihydroxyanthraquinone-2-sulfonic acid phenylstcr thus obtained can optionally be recrystallized from glacial acetic acid; he fies Polyester fibers in orange tones with very good lightfastness and sublimation fastness.

Example 25

10 parts of strand material made of Polyäthylcnglykolterephthalat are in a liquor of 600 parts of water, 0.1 part finely divided 1,4-diaminoanthraquinone - 2 - sulfonic acid - (3 '- chloro - 6' - methylphenyD-ester. which was obtained according to Example 1. 3.4 parts of a mixture of .v, m-, p-cresotinic acid methyl ester and 0.6 parts of a mixture of equal parts aralkyl sulfonate and a non-ionic one Polyglycol ethers after the addition of sulfuric acid until a pH value of 4.5 has been set Stained at 96 to 98 for 2 hours. Then ge rinsed and dried. The fastness to rubbing can be improved if you put it in a low-boiling bath 5.5 parts of 38 Be sodium hydroxide solution, 2 parts of sodium dilhionite and 1 part of a poly per 1000 parts of water contains glycol ethers of an acid amide, post-treated for 10 to 30 minutes. One gets a reddish cast blue coloring with good to very good authenticity properties, especially a very good subli mierechtheit.

The dyes obtained according to Example 2 and 22 to 24 can also be colored.

Example 26

10 parts of a fabric made of Polyaihyleneglykolten phthalate are in a liquor with a pH of 4.5 at 400 parts of water and 0.1 part of 1,4 - diamino - anthraquinone - 2 - sulfoi present in the finest Veneilur

309611/21

acid - (2 ', 4' dichlorophynyl) - ester, according to the example 13 was obtained, and 0.3 parts of a mixture of equal parts and aralkyl sulfonate of a non-ionic polyglycol ether 2 hours bc; 120 to 130 "colored. After rinsing and Drying gives a brilliant reddish blue coloration with good to very good natural properties, especially a very good Sublimicrechtcit. Likewise, those according to Examples 1 to 10. Color 12 to 20 and 22 to 24 obtained dyes.

Example 27

A fabric made of polyethylene glycol crephthalate fibers is impregnated with a liquor on the padder, the in 1000 parts 20 parts of the finely divided 1,4-diamino-anthraquinone-2 - sulfonic acid c - (3 '- chloro · 6' - methyl - phenyl) - ester, which was obtained according to Example 1, and 10 parts ThermosolhilfsmiUel, especially a polyethylene ether, such as. B. in Belgian patent specification 615 102 described, contains.

The fabric is then squeezed off to a weight increase of 70% and dried in a floating nozzle dryer or in a drying cabinet at 80 to 120 °. The fabric is then treated with hot air in a soann frame or in a hot-flue nozzle for about <0 seconds at 190 to 200 °, then rinsed, possibly reductively aftertreated and dried. The reductive aftertreatment for the purpose of removing dye components adhering to the surface of the fibers can be carried out in such a way that the fabric is mixed with 3 to 5 ccm / liter sodium hydroxide solution at 38 ° Bc and 1 to 2 g / liter hydrosulfite (concentrated) at 20 to 25 ° containing liquor enters, heated to 70 ° within about 15 minutes and left at 70 ° for a further 10 minutes. It is then rinsed with hot water, acidified with 2 to 3 cc / liter of 85% formic acid at 50 °, rinsed and dried. A clear, reddish-tinged blue dyeing is obtained, which is distinguished by its high dye yield and its good build-up capacity and good to very good fastness properties.
The dyes obtained according to Examples 2 to 20 and 22 to 24 can also be colored.

Example 28

10 parts of a synthetic polyamide fabric are in a liquor containing 400 parts of water, 0.2 parts of 1,4-diamino-anthraquinone-2-sulfonic acid phenyl ester, which was obtained according to Example 3, in fcinverteilte form and 0.2 parts of a conventional one Contains dispersant, slowly heated to boiling and colored at the boil for 1 hour. Subsequently is rinsed, if necessary lightly soaped and dried. A reddish blue coloration is obtained of good fastness to washing, light and rubbing.

Likewise, according to Example 1, 2.4 to Coloring 20 and 22 to 24 obtained dyes.

Claims (1)

Claims: 1. Anthraquinone substances of the formula Y, OX ₁ ¹ "'SO ₂ -OR in which X and X _{2 are} a primary amino group or a hydroxyl group, Y ₁ and Y _{2 are} hydrogen, a primary amino group or a hydroxyl group and R is optionally substituted by lower alkyl, methoxy, chlorine, bromine, methylmercapto, nitro, trifluoromethyl, phenyl, acetyl, Carbomethoxy or carboxyl-substituted phenyl radical or a naphthyl radical.